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使用可见光激发,通过溶胶-凝胶共价键接枝镧系元素[Sm(3+)、Yb(3+)、Nd(3+)、Er(3+)、Pr(3+)、Ho(3+)]β-二酮衍生物的近红外和可见发光。

Near infrared and visible luminescence from xerogels covalently grafted with lanthanide [Sm(3+), Yb(3+), Nd(3+), Er(3+), Pr(3+), Ho(3+)] β-diketonate derivatives using visible light excitation.

机构信息

Research Center of Nano Science and Technology, Shanghai University , Shanghai, Shanghai 200444, P. R. China.

出版信息

ACS Appl Mater Interfaces. 2013 Oct 9;5(19):9585-93. doi: 10.1021/am402529w. Epub 2013 Sep 24.

Abstract

A series of ternary lanthanide β-diketonate derivatives covalently bonded to xerogels (named as Ln-DP-xerogel, Ln = Sm, Yb, Nd, Er, Pr, Ho) by doubly functionalized alkoxysilane (dbm-Si) was synthesized in situ via a sol-gel process. The properties of these xerogel materials were investigated by Fourier-transform infrared (FT-IR) spectroscopy, field-emission scanning electron microscopy (FE-SEM), diffuse reflectance (DR) spectroscopy, thermogravimetric analyses, and fluorescence spectroscopy. The data and analyses suggest that the lanthanide derivatives have been covalently grafted to the corresponding xerogels successfully. Of importance here is that, after excitation with visible light (400-410 nm), the xerogels all show characteristic visible (Sm(3+)) as well as near-infrared (NIR; Sm(3+), Yb(3+), Nd(3+), Er(3+), Pr(3+), Ho(3+)) luminescence of the corresponding Ln(3+) ions, which is attributed to the energy transfer from the ligands to the Ln(3+) ions via an antenna effect. Exciting with visible light is advantageous over UV excitation. Furthermore, to the best of our knowledge, it is the first observation of NIR luminescence with visible light excitation from xerogels covalently bonded with the Sm(3+), Pr(3+), and Ho(3+) derivatives. Compared to lanthanide complexes (Ln = Er, Nd, Yb) functionalized periodic mesoporous organosilica (PMO) materials that exhibit similar optical properties reported in our previous work, the Ln-DP-xerogel (Ln = Sm, Yb, Nd, Er, Pr, Ho) in this case offer advantages in terms of ease of synthesis and handling and potentially low cost for emerging technological applications. Development of near-infrared luminescence of the lanthanide materials with visible light excitation is of strong interest to emerging applications such as chemosensors, laser systems, and optical amplifiers.

摘要

一系列三元镧系β-二酮衍生物通过双官能化烷氧基硅烷(dbm-Si)共价键合到气凝胶上(命名为 Ln-DP-xerogel,Ln = Sm、Yb、Nd、Er、Pr、Ho),这是通过溶胶-凝胶过程原位合成的。通过傅里叶变换红外(FT-IR)光谱、场发射扫描电子显微镜(FE-SEM)、漫反射(DR)光谱、热重分析和荧光光谱研究了这些气凝胶材料的性质。数据和分析表明,镧系衍生物已成功共价接枝到相应的气凝胶上。重要的是,在用可见光(400-410nm)激发后,所有气凝胶都显示出相应 Ln(3+)的特征可见光(Sm(3+))以及近红外(NIR;Sm(3+)、Yb(3+)、Nd(3+)、Er(3+)、Pr(3+)、Ho(3+))镧系离子的发光,这归因于配体通过天线效应将能量转移到 Ln(3+)离子上。用可见光激发比用紫外光激发更有利。此外,据我们所知,这是首次观察到用可见光激发共价键合 Sm(3+)、Pr(3+)和 Ho(3+)衍生物的气凝胶的近红外发光。与我们之前工作中报道的具有类似光学性质的镧系配合物(Ln = Er、Nd、Yb)功能化的周期性介孔有机硅(PMO)材料相比,这种情况下的 Ln-DP-xerogel(Ln = Sm、Yb、Nd、Er、Pr、Ho)在合成和处理方面具有优势,并且在新兴技术应用方面具有潜在的低成本优势。发展用可见光激发的镧系材料的近红外发光对于新兴应用领域如化学传感器、激光系统和光放大器具有强烈的兴趣。

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